WO1995034613A1

WO1995034613A1 - Lubricating oil composition with excellent stability, process for producing the same, and method of refining the same

Info

Publication number: WO1995034613A1
Application number: PCT/JP1995/001174
Authority: WO
Inventors: Fumihiko Yamaguchi; Eiji Seki; Ikuo Yamamoto; Tatsuya Otsuka; Hideki Hara
Original assignee: Daikin Industries, Ltd.
Priority date: 1994-06-14
Filing date: 1995-06-12
Publication date: 1995-12-21
Also published as: MY114176A; AU2631095A

Abstract

A lubricating oil composition containing a compound represented by general formula (I) and having an excellent stability, wherein n represents an integer of 0 to 5; R1a represents CF¿2?CF2H or H; and R?2 to R7¿ represent each a C¿1?-C100 aliphatic group which may be partially fluorinated, provided when R?1a¿ is H, any of R?2, R5 and R6¿ is fluorinated. The composition is excellent in the compatibility with fluoroalkanes and suitable for a refrigerating system using a fluoroalkane, particularly a hydrofluoroalkane, as the refrigerant. It has an excellent lubrication performance and a high heat stability even when used alone or in a refrigerating system using a fluoroalkane as the refrigerant. It has the effects of oxidation inhibition, deacidification, and dehydration.

Description

Specification

Lubricating oil composition having excellent stability, method for producing and refining treatment method

Technical field

The present invention relates to a lubricating oil composition having excellent stability, and a method for producing and refining the composition.

Background technology

Conventionally, as the refrigerating machine oil, mineral oils such as paraffinic and naphthenic oils, and synthetic oils such as alkylbenzene oils and ester oils have been known. These oils are mainly composed of trichloro mouth fluorometan (fluoro-11), dichlorodifluorometane (fluoro-11), and chlorodifluoromethane. It is used in refrigerators that use (Front 122) as a refrigerant. However, in recent years, when released into the atmosphere, chlorine-containing fully halogenated hydrocarbons such as fluorocarbons 11 and 11 or fluorocarbons 12 It has been pointed out that chlorine-containing chlorinated hydrocarbons destroy the ozone layer in the stratosphere, resulting in serious adverse effects on living systems on the earth, including humans. Therefore, the use and production of certain fluorocarbons, such as fluorocarbons 11, 11 and 12, may be restricted by international agreements. Has reached.

Cooling instead of Fluorine 11, Fluorine 12 and Fluorine 22 As a medium, CH ₂ FCF ₃ (one fluorocarbon),

CF ₂ H ₂ (Front 3 2), CF „HCF ₃ (Front 1 2 5), CF ₃ H (Front 1 2 3) ヽ CF ₃ CH ₃ (Front 1 4) 3a) and other hydrogen-containing fluorocarbons have been proposed, which do not have the potential to destroy the ozone layer, but have very low compatibility with conventional refrigerating machine oils. If conventional refrigeration oil is applied to a refrigeration system using hydrogenated hydrocarbon as a refrigerant, the durability of the compressor will decrease and the compressor will not be able to operate in a short time, or the cooling capacity and coefficient of performance of the refrigeration system will be remarkable. Or lower.

Therefore, it is conceivable to use fluorine-containing oil (fluorine-based oil), which is a compound that is considered to be highly compatible with hydrogen-containing fluorine-containing hydrocarbons, as the refrigerating machine oil. These are Fomblin (a trademark of Montefluos), Krytox (a trademark of DuPont), Demmnum (a trademark of Daikin Industries, Ltd.). It is marketed under trade names such as [trademark of a corporation], and has, for example, the following repeating units as its main structure (where n and m are each an integer of 1 or more).

_{- (C (CF) FCF 2} - 0) - - (CF 2 CF 0 CF 9 - 0) - _{_{- (C (C F 3)}} FCF 2 - 0) n - (CF 2 - 0) m - However, these known full Tsu Motokei for oil, always be satisfactory in terms of compatibility with the refrigerant It is not. This is probably because these fluorine-based oils contain little or no hydrogen in their structures. In addition, these fluorine-based oils are difficult to put to practical use because the monomer corresponding to the repeating unit in the structure is expensive.

Therefore, when the above-mentioned hydrogen-containing fluorine-containing hydrocarbon is used as the refrigerant, in order to improve the compatibility between the refrigerant and the refrigerating machine oil, the fluorine-containing fluorine is used together with the fluorine. It is effective to use basic oils as refrigerating machine oils, and the development of simple manufacturing methods is considered important for practical use.

The hydrogen-containing fluorine-based oils are described in Japanese Patent Application Laid-Open Nos. 3-250491, 3-7798, etc., and are described in these publications. However, there is a drawback that a compound having a perfluoropolyether bond is used as a basic unit, and a monomer used as a raw material is expensive. In addition, since the fluorine-containing portion is basically based on the COF terminal, the reaction product with the hydrocarbon compound becomes an ester, which is susceptible to hydrolysis. On the other hand, when synthesizing a compound other than an ester, the terminal COF of the fluorine-containing compound can be

Must convert to one CH ₂ 0 H, there is a disadvantage that the reaction is multistage. Then, the refrigerating machine oil to be synthesized will be expensive and it will be difficult to put it to practical use. In addition, the polyester compounds disclosed in JP-A-3-12891, JP-A-3-17991, and the like also have a phase with fluoro-134a. Although it is said to be excellent in solubility, it contains an ester group, so it has high hygroscopicity, is easily decomposed by hydrolysis and the like, has a problem in durability, and has excellent stability. The development of the composition and the method of its manufacture are considered important.

An object of the present invention is to use a hydrogen-containing halogenated hydrocarbon as a refrigerant, which has good compatibility with a hydrogen-containing halogenated hydrocarbon and is stable. It is an object of the present invention to provide a lubricating oil composition suitable for the present invention, a method for producing the same, and a method for refining.

Disclosure of the invention

The present invention provides a compound represented by the general formula [1]:

(Where n is an integer from 0 to 5; R ^la is CF ₉ CF ₉ H or '

H, RR "is an aliphatic group having 1 to 100 carbon atoms or an aliphatic group having 1 to 100 carbon atoms, a part of which is substituted with a fluorine atom (when ^Ria is H, .R ² , R ⁵ or R ⁰ has a fluorine atom in any one of the above groups.) A lubricating oil composition, a refrigerating machine oil composition and a fluorine-based lubricating composition comprising the compound [1] It relates to an oil composition.

The present invention also provides a compound [1] and a general formula [2]:

(Where m is an integer of 1 to 6; R ^lb and R ^le are each CF ₂ CF ₂ H or H, and R ^1d and R ^LC may be different from each other; R ^{8 to} R ^U is an aliphatic group having 1 to 100 carbon atoms or an aliphatic group having 1 to 100 carbon atoms partially substituted by a fluorine atom (R ^lb and R ^le simultaneously represent H A fluorine atom having a fluorine atom in either of R ⁹ or R ^1D )), a highly stable lubricating oil composition, a refrigerator oil composition, and a mixture of the compound [2] It relates to a nitrogen-based lubricating oil composition.

Further, the present invention provides a mixture of compound [1] and compound [2] and an additive, a fluorine-containing additive, a thickener, and a fluorine-containing thickener. TECHNICAL FIELD The present invention relates to a lubricating oil composition, a refrigerator oil composition, and a fluorine-based lubricating oil composition having excellent stability. Further, the present invention has 1 to 5 carbon atoms partially or completely substituted with at least one atom of chlorine or fluorine, and has a temperature of 180 ° C. The present invention relates to a highly stable lubricating oil composition, a refrigerating machine oil composition, and a fluorine-based lubricating oil composition used together with a saturated hydrocarbon having a standard boiling point in the range of up to 150 ° C. Furthermore, the present invention provides a compound of the formula [3]: 2 H

A compound [3] represented by the formula [4] 2H

Compound (4) and Formula (5)

CH ₀ CH

J L 6

HCF _n CF _2- ^ OCH ₂ .C— CI- I ₉ ^ ~ OCF ₉ CF ₂ H CII _n OC FCF ₂ H And [5].

Further, the present invention provides a highly stable lubricating oil composition, a refrigerator oil composition and a fluorine-containing composition using compound [3], compound [4] or compound [5] as a thickener. It relates to a lubricating oil composition.

Furthermore, the present invention relates to a method for producing and purifying compound [1] or a mixture of compound [1] and compound [2], compound [3], compound [4] and compound [5].

The lubricating oil composition, the refrigerating machine oil composition and the fluorine-based lubricating oil composition containing the compound [1] have an antioxidant or deoxidizing / dehydrating effect, and have excellent stability in lubricating oil or refrigerating machine oil. It is. The content (weight ratio) of the compound [1] in the composition of the present invention is from lppm to: L00%, preferably from 5 ppm to 80%, more preferably 10 ppm. ~ 60%, particularly preferably 1% ~ 30%.

As a compound to be mixed with compound [1], compound [2] is preferable because it can be produced at the same time, but is not limited thereto. However, a composition obtained by mixing the compound [1] with a compound synthesized using a fluorine atom-containing fluororefin as a raw material has low thermal stability. Therefore, it is preferable that the composition of the present invention does not substantially contain a compound synthesized using a chlorine atom-containing fluororefin as a raw material.

In general, starting materials (having no halogen atom When a chlorine atom-containing fluororefin is used as a reaction raw material for introducing a halogen atom, the lubricating oil composition obtained has reduced thermal stability. On the other hand, as a result of research, the present inventor has shown that extremely high thermal stability is obtained by using tetrafluoroethylene (TFE), which is a fluorine-free fluorofluorin, as a reaction raw material. It was found to be a lubricating oil composition.

Furthermore, a compound synthesized using a chlorine atom-containing fluororefin as a raw material does not improve the thermal stability even in a mixed system with the compound [1]. On the other hand, it was found that the compounds other than the compound synthesized using the chlorine atom-containing Fluoro-Refin as a raw material, the mixture with the compound [1] showed high thermal stability. Therefore, it is not preferable to include a compound synthesized using chlorine-containing fluororefin as a raw material in the composition of the present invention. The content of the compound synthesized using the chlorine-containing fluororefin of the composition of the present invention as a raw material is at most 50% by weight, preferably at most 30% by weight, and furthermore It is preferably not more than 10% by weight, particularly preferably not containing substantially.

Further, the aliphatic group substituted with aliphatic groups and some corresponding to R ² ~ R ^U by full Tsu atom is an oxygen atom, may have an unsaturated bond, and with their aliphatic group Are many For example, — CH ₂ —,-CH ₂ CH ₂

-CH ₂ (OCH ₂ CH ₂ ) _x- ,

- Ji _{CH 2 (0 ((: 11} 3) 11 (:. 11 2) (, is 1-3 integer 0 _{7), _ CH 2 0 CF} 2 CF 2 H, - CH 2 OH, one CH, one CH ₉ CH _{3 and the} like can be mentioned, but the present invention is not limited thereto.

Lubricating oils with excellent stability according to the present invention include thickeners, viscosity index improvers, detergent / dispersants, extreme pressure additives, antiwear agents, oiliness improvers, antioxidants, antioxidants, and corrosion inhibitors. , Antifoaming agents, emulsifiers, moisture release agents, pour point depressants, metal deactivators, antiseptic agents and other additives usually added to lubricating oils. It can be used by adding the above. As these additives, a fluorine-containing additive may be used, and various types of aliphatic and aromatic fluorine-containing additives can be used. The additive amount of the additive may be a commonly used amount, and is 0.1 l pp n! 995% by weight, preferably lppm〜90% by weight, but not limited thereto.

Examples of the thickener in the present invention include a fluorine-based thickener and a non-fluorine-based thickener. Examples of the fluorine-based thickener include fluorine-containing aliphatic compounds such as perfluoropolyether and perfluoroalkylpropoxy, and fluorine-containing aromatic compounds. is not. Non-fluorinated thickeners include poly (oxyethylene, oxypropylene) glycol, polyoxyethylene glycol, poly (oxyethylene, oxypropylene) glycol monoether, and poly (ethylene glycol). Oxyethylene glycol monoether, poly (oxyethylene, oxypropylene) glycol monophenyl ether, polyoxyethylene glycol-monomonophenyl ether, poly (oxyethylene, oxypropylene) glue Cole bisphenyl ether, polyoxyethylene glycol Coal bisphenyl ether, polyoxyethylene glycol , Oki Although ethylene) glycol, and the like not limited to this.

The compound [1] in which n is 1 or more and the compound [2] in which m is 2 or more have a high viscosity, and the viscosity can be improved by adding them. Such compounds include, for example, 5,5,9,9-tetrax (3 ', 3', 4 ', 4'-tetrafluoro-2'-oxabutyl) 1-1,1,2,2 2,1,2,12,1,3,1 3—3,7,11 1 Trioxatridecane, 3— (3 ', 3', 4 ', 4' Trafluorol 2--oxoxabutyl) 1 3 — (4 ', 4' bis) (3 ", 3", 4 ", 4"-tetrafluoro-2 "-oxabutyl) 1 7 ', 8', 8 '-tetrafluoro-2', 6 '-dioxaoctyl) 1 Oxetane (compound

(3))), but not limited to this.

The amount of the thickener to be added is 0.1 to 90% by weight, preferably 1 to 80% by weight, but is not limited thereto. It has 1 to 5 carbon atoms partially or completely substituted with at least one atom of chlorine or fluorine in the present invention, and is 180 ° C. to 150 ° C. Saturated hydrocarbons having a standard boiling point in the C range include, for example, 1,1,1,2—tetrafluoroethane (HFC—134a), 1,1,2,2- Traflouroethane (HFC-134), difluoromethan

(HFC-32), 1, 1, 1, 1, 2, 2—Pentad Fluoroethane (HFC-125), Trifluorometan (HFC-123), 1, 1, 1 1,1-Difluoroethane (HFC-152a), 1,1,1,2,3,3,3 —Hepeven Fluoropropane (HFC-22) 7 ea), 1,1,1,2,2,3,3 —Hep Even Fluoropropane (HFC—227 Ca),

C F C H,

3 2 ^CF 3 c FCHFCHF ₂ ,

Three

CFCFCH ₂ F, CF

3 2 2 ^HC ^F 2 ^CHF 2 ヽ

C F C H C H F C F

3 2 2, 3 ^CF 2 ^CH 3 ^s CF ₂ HCF ₂ CH ₂ F, CF ₃ CF _% CH _g ,

CF ₃ CHFCHFCF ₃ ,

Various lower fluorinated alkanes such as fluorinated methane such as CF ₃ CHFCHFCF ₂ CF _{3 and the} like, and propane fluorinated and butane fluorinated can be exemplified, but not limited thereto.

Total weight of refrigerant in refrigeration system Weight ratio of total lubricating oil is usually in the range of 99/1 to 1/99, preferably 991-

It is in the range of 90/90, particularly preferably in the range of 99/1 to 280/80.

A typical method for synthesizing compound [1] is U.S. Pat.

Methods such as those described in the specification of 3, 210, 298 can be mentioned.

However, according to the method of the present invention, compound [1] can be obtained by reacting compound [6] with tetrafluoroethylene (TFE) as a raw material, and furthermore, The compound [2] can be obtained at the same time.

[6]

[1]

(In here, n = 0 to 5 integer; m =. 1 to 6 integer; R ^la, R ^lb and R ^le is Ri CF ₂ CF ₉ 2 H or H Der respectively, R ^la, R ^lb and R ^le may be different from each other; R ² ~

R ¹¹ is an aliphatic group having 100 carbon atoms or an aliphatic group having 100 carbon atoms in which a part thereof is substituted by a fluorine atom (R ^la is

In the case of H or when R ^lb and R ^le are simultaneously H, a fluorine atom is present in any of R ² , R ³ , R ⁶ , R ^J or R ^1Q ©); R ^{12 to} R ¹⁵ are Carbon number; ~ 100 aliphatic groups).

1 ² to 1 ^ ¹⁵ aliphatic group of from 1 to 1 0 0 carbon number of, rather'll have an oxygen atom or an unsaturated bond, for example, - CH ₂ -, one CH ₀ CH ₂ -ヽover CH ₂ (0 CH ₂ CH) _χ- (X is an integer from 1 to 30),

CH ₂ (〇 C (CH ₃ ) HCH ₂ ) _y (y is 1-3

0), CH ₂ 〇 H, -CH ₀ CH ₂ OH, etc. Four

It is. The compound [6] can be variously classified depending on the types of R ¹² to R ^{15. As} an easily available compound, specific examples include a compound represented by the formula:

CH ₂ OH

HOCH ₂ ― C— CH ₂ OH

CH ₂ OH

CH ₂ OH CH OH

I ²

HOCH ₂ ― C— CH ₂ OCH _2- ■ C— CH OH

I ² ,

CH ₂ OH CH ₂ OH

CH ₂ CH ₃

^CH 2 ^CH 3

HOCH ₉ ― C— CH ₂ OCH ₂ -C— CH ₂ OH

CH ₂ OH CH _n OH

The compounds represented by the following formulas are preferred, but do not limit the present invention. According to the method of the present invention, the formula [8]:

Is reacted with TFE using the compound [8] By doing so, compound [4] and compound [5] can be obtained.

In the reaction of compound [6] with TFE and the reaction of compound [8] with TFE, a solvent is often used, and a non-protonic polar solvent can be used. It is preferable to use a 1- to 0.5-fold volume, preferably 0.5- to 0.5-fold volume, and more preferably a 1- to 5-fold volume. Specific examples of the solvent include DMF, DMSO, NMP, sulfolane, diglyme, triglyme, ether, THF, chloroform, and dichloromethane. In addition, only compound [2] can be produced by using methylethyl ketone, acetate, or the like. Water may be added to the reaction solution.

When HF is by-produced as a reaction catalyst, a basic catalyst may be used as a scavenger. In this case, it is preferable to use 0.01 to 10 equivalents, preferably 0.01 to 5 equivalents, and more preferably 0.1 to 2 equivalents to any of the raw materials. . By changing the amount of the base, the ratio of the compound [1] and the compound [2] contained in the obtained mixture can be changed. Is a specific example of a basic catalyst, KOH, N a OH, K 2 C_〇 _3, N a ₂ C_〇 _3, N a HC o inorganic base such as _3, Application Benefits Echirua Mi down, Application Benefits Puchirua Mi And organic bases such as

The reaction temperature is −10 to −200, preferably 0 to 150 ° C., particularly preferably 10 to 120 ° C., and the reaction pressure is not particularly limited. The reaction can be carried out preferably at 0 to 20 kg / cm ² G, particularly preferably at 0 to LO kgZ cm ² G. The reaction time is 0.5 to 100 hours, preferably 2 to 50 hours. Further, the molar ratio of TFE / compound [4] of the reaction raw material is preferably from 0.01 to 20, more preferably from 0.5 to 10, and further preferably from 0.5 to 5. . In either case, it is possible to drop or blow one of the raw materials, but this is not a limitation.

'After the reaction, purification can be performed by a usual method. For example, the reaction mixture is quenched into a large amount of water, and the separated organic layer is washed with an acid, alkaline, and saturated saline. It may be extracted with a solvent that is not compatible with water (1,1-dichloro-11-fluorobenzene (HCFFC14lb), dichloromethane, or cro-holm). The obtained organic layer is dried over anhydrous sodium sulfate or magnesium sulfate, filtered, and the solvent is distilled off under reduced pressure to obtain the desired compound [1] and compound [2]. be able to. If necessary, it can be purified by distillation under reduced pressure or column chromatography.

High-purity fluorine-containing lubricating oil composition by the above synthesis method Can be obtained, but the total acid value may be unsatisfactory due to the effect of trace impurities (eg, carboxylic acid). Since the compound of the present invention originally has a deoxidizing effect, the total acid value does not increase during use of the compound of the present invention, but it may be necessary to keep the initial total acid value low. Therefore, as a result of studying a treatment method for lowering the total acid value, the following method was found.

That is, the high-purity fluorine-containing lubricating oil composition obtained by the above-mentioned method was used for silica gel, aluminum, activated carbon, charcoal, bone charcoal, zeolite, activated clay, bauxite, magnesia, gay Low in inorganic or organic sorbents such as alumina, magnesium magnesia, aluminum magnesia, aluminum gel, aluminum hydroxide sodium hydroxide, magnesium aluminum hydroxide carbonate, etc. In addition, they have found that a fluorine-containing lubricating oil composition having a reduced total acid value can be obtained by contact with one kind.

As a treatment method, the adsorbent may be dispersed in the lubricating oil composition of the present invention or a solution thereof, or the lubricating oil composition of the present invention or a solution thereof in a column using the adsorbent as a filler. May be subjected to a catalytic purification treatment. When filtering the adsorbent, a filter aid may be used.

Further, the lubricating oil composition of the present invention comprises a working fluid, a defoamer, a buffer, It can also be used for oils, surface treatment agents, release agents, emulsifiers for cosmetics, and surface modifiers.

The invention's effect

1. The lubricating oil composition of the present invention is used as a substitute for a chlorine atom-containing refrigerant such as CFC12 (dichlorodifluoromethane) and HCFC22 (chlorodifluoromethane) from the viewpoint of environmental protection. And promising fluorinated alkanes, such as hydrofluorenes such as hydrofluoroethane, and more preferably HF.

C-134a (1, 1, 1, 2—tetrafluoroethane), HFC—32 (difluoromethan), HFC—125 (1,1,1,2,2—pentafluoroethan) ) Excellent compatibility with fluorinated alkane-based refrigerants suitable for refrigeration systems that use such as refrigerants.

2. The lubricating oil composition of the present invention may be used alone or in the presence of a chlorine atom such as CFC12 (chlorodifluoromethane) or HCFC22 (chlorodifluoromethane) due to environmental protection problems. Alcohol fluorides, which are promising alternatives to contained refrigerants, are preferred, such as, for example, hydrofluorene or chlorofluorophenol, and more preferably HFC-134a (1, 1, 1, 2-tetrafluoroethane), HFC-32 (difluoromethane), HFC-125 (1, 1, 1, 2, 2, 2-pentafluoroethane) etc. as refrigerant Used during refrigeration system Even so, its lubrication performance is excellent.

3. The lubricating oil composition of the present invention has high thermal stability even when the lubricating oil is used alone or in the presence of a refrigerant.

4. The lubricating oil composition of the present invention has antioxidant, deoxidizing, and dehydrating effects.

Example

Examples and comparative examples are given below to further clarify the present invention.

Example 1

To a place where pentaerythritol (500 g), KOH (480 g) and DMSO (1.5 L) were added to a 6-L autoclave and subjected to nitrogen substitution and reduced pressure, tetra Fluoroethylene (150 g) was injected. Each time tetrafluoroethylene was consumed, it was further introduced and reacted at 80 ° C. After completion of the reaction, the reaction mixture was extracted with HCFC-141b (1,1-dichloro-1-fluorobenzene) and washed with water, a 1N aqueous solution of HC1 and saturated saline. The organic layer was dried over N a _n S 0 _4, filtered, and then concentrated under reduced pressure at 5 0 ° C to give the oily compound [Oil A] (1 6 0 0 g ). The obtained oil A is a compound a corresponding to the case where n = 0 in the general formula [1]:

And C (CH ₂ CF ₂ CF ₉ H) _4, and the weight ratio of compound a / C (CH ₂ 〇CF ₂ CF ₂ H) ₄ was 3862.

Example 2 6 L autocrepe was charged with pentaerythritol (70 Og) KOH (850 g) and DMSO (1.5 L), and the atmosphere was replaced with nitrogen. 2100g). Each time tetrafluoroethylene was consumed, it was further introduced and reacted at 80 ° C. After completion of the reaction, the reaction mixture was extracted with HCFC-141b, and washed with water, a 1N aqueous solution of HC1 and saturated saline. The organic layer was dried over Na ₂ S, filtered, and concentrated under reduced pressure at 60 ° C. to obtain an oily compound [oil B] (180 g: compound a,

C (CH ₂ OCF ₂ CF, H) ₄ = 5 4/4 6) ₀ Example 3

To a place where 200 ml of autoclave was filled with Penyu erythritol (20 g), KOH (19 g) and MEK (60 ML), and the atmosphere was replaced with nitrogen and the pressure was reduced, Trafluroethylen (60 g) was injected. Every time tetrafluoroethylene was consumed, it was further introduced and reacted at 80 ° C. After completion of the reaction, the reaction mixture was extracted with HCFC-141b, and washed with water, a 1N aqueous solution of HC1 and saturated saline. The organic layer was dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure at 50 ° C. to obtain an oily compound [oil C] (65 g

Compound a ZC (CH ₂ 0 CF _n CF ₉ H) _A = 0.0 1 9 9.99 9) o Example 4

To a place where 200 ml of autoclave was charged with Penyu erythritol (20 g), KOH (1.9 g) and DMSO (60 ML), and the atmosphere was replaced with nitrogen and the pressure was reduced, the temperature was lowered. Trafluroethylene (60 g) was injected. Each time tetrafluoroethylene was consumed, it was further introduced and reacted at 80 ° C. After the completion of the reaction, the mixture was extracted with 11 × 14 11), and washed with water, an aqueous solution of HC1 IN and saturated saline. Organic layer

After drying over Na ₂ SO, filtration and concentration at 50 ° C under reduced pressure, an oily compound [oil D] was obtained (63 g: compound a / C (CH ₂ OCF ₂ CF ₂ H)) = 4/96).

Example 5

To a place where 1 L autoclaved was charged with dipentyl erythritol (150 g), KOH (39) and DMSO (450 ML), and the pressure was reduced by purging with nitrogen. Tetrafluorene (433 g) was absorbed. Each time tetrafluoroethylene was consumed, it was further introduced and reacted at 80 ° C. After completion of the reaction, the mixture was extracted with HCFC-141b and washed with water, a 1N aqueous solution of HC1 and saturated saline. The organic layer was dried over N a ₂ S 0 _4, filtered, and then concentrated under reduced pressure at 5 0 ° C to give an oily of compound [Oiru E] (4 3 5 g) . The obtained oil E is a compound corresponding to the case where n = 1 in the general formula [1]. Compound, which corresponds to compound [3] e 2 H

And compound f

CH ₂ OCF ₂ CF ₂ H

HCF CF ₂ — 0CH ₂ -C— CH ₂ --OCF ₂ CF H

CH ₂ OCF ₂ CF ₂ H

And the weight ratio of compound e to compound f was 33 to 67.

Compound e is ^{H- NMR, 19 F (CDC 1} .) - was confirmed I by the MR (CFC 1 _3).

1

H-NMR (CDC 1) δ (pm): 3.5 (s, 2H) 3.6 (s, 2H), 3.9 (s, 6H) 4.2 (s2H), 4 . 4 (s, 4 H) , 5. 6 (t, 4 H) 19 F - NM R (CFC 1 3) δ (ppm): - 1 3 7. 5 (dt, 8 F), - 9 3. 1 (m, 6 F), — 9 2.3 (m, 2 F) Example 6 The oil D (30) obtained in Example 4 was added to the oil D (30) obtained in Example 5. The obtained oil E (20 g) was added to obtain an oily compound (oil F) (50 g).

Example 7

1 0 0 cc auto click Leeb di Application Benefits main Chirorupurono, ⁰ emissions (1 5 g), the KOH (6 g) and DMSO (4 5 ml) This and was reduced pressure for nitrogen substitution put the filtrate, te Trafluroethylene (30 g) was injected. Each time tetrafluoroethylene was consumed, it was further introduced and reacted at 80 ° C. After completion of the reaction, the mixture was extracted with HCFC-141b, and washed with water, a 1N aqueous solution of HC1 and saturated saline. The organic layer was dried over N a ₂ S 〇 _4, filtered, and concentrated in vacuo at 5 0 ° C to give an oily of compound [Oil G] (3 6 g). The obtained oil G is a compound corresponding to the case where n = 1 in the general formula [1], and a compound g corresponding to the compound [4]:

0- CH ₂ 〇CF ₂ CF ₂ H

-CH „OCH, -C-CH ₂ OCF ₂ CF ₂ H

Two

CH _n CH ₃

CH ₂ CH ₃ and the compound corresponding to compound [5] h:

CH ₂ CH

HCF ₂ CF _2- ^ OCH ₂ C— CH ₂ ^ -7T-OC F ₀ CF ₂ M

CII ₂ OCF ₂ CF ₂ H And the weight ratio of compound h was 17 Z83. Compound g is one NMR (CDC 1), ^U F-NMR

It was confirmed by (CFC 1 ₃₎

_{. H - NMR (CDC 1 3} ) δ (ppm): 0. 8 (t, 6 H) 1. 5 (q, 2 H), 1. 7 (q, 2 H) 3. 3 CS, 2 H) , 3.5 (s, 2H), 3.9 (s, 4H), 4, 3 (d, 2H), 4.

4 (d, 2 H), 5. 6 (t 2 H) 19 F - NMR (CFC 1 3) δ (ppm) one 1 3 7. 5 (dt, 4 F), 9 3. (m, 4 F )

19

Compound h is H—NMR (CDC 1) F-NMRR

It was confirmed I'm in (CFC 1 _3).

1

H-NMR (CDC 10) δ (ppm): _0.8 (t, 6 H) 1.5 (q, 4 H),

3.3 (s, 4 H). 3. 9 (s, 8 H), 5.6 (t,

4 H)

19 F-NMR (CFC 1) δ (m): −1 37 5 (d 8 F), 93.1 (m, 8 F) Example 8 The oil G (4.5 g) obtained in Example 7 was added to the oil D (45.5 g) obtained in Example 4, and the oily compound (Oil H) (50 g) was added. I got

Example 9

Oil C obtained in Example 3 was distilled under reduced pressure, and Compound a was isolated to obtain Oil I.

Comparative Example 1

Trimethylolpropane (30 g), NaOH (2 g) and DMSO (200 cc) were placed in a 500 ML autoclave, and the atmosphere was replaced with nitrogen. Lorori trifluoroethylene (100 g) was injected. Each time the fluoro mouth trifluoroethylene was consumed, it was further introduced and reacted at 80 ° C. After completion of the reaction, extraction was performed with HCFC-141b, and the extract was washed with water, a 1N aqueous HC1 solution, and saturated saline. Organic layer

Dried N a ₂ S 0 _4, filtered, and then concentrated under reduced pressure at 5 0 ° C to give the oily compound [Oil X] (74 g).

Compatibility test

Compatibility test 1

The compounds obtained in each example were tested for compatibility with HFC-134a. The compound (oil) obtained in each of the target examples was placed in a Pyrex test tube with an inner diameter of 8 mm and a length of 200 mm, and the inside of the test tube was evacuated and cooled with liquid nitrogen. It was filled with 1 g of HFC-134a (refrigerant) (ratio of oil-Z refrigerant is 20/80 wt%). After charging the refrigerant, the test tube was sealed, placed in a temperature-controlled thermostat, and after the temperature reached equilibrium, the compatibility with the refrigerant was judged visually and the phase separation temperature at a low temperature was measured. Table 1 shows the phase separation temperatures at low temperatures.

table 1

Compound Phase separation temperature (° C)

Oil A 50 or less

Oil B 150 or less

Oil C 150 or less

Oil D 50 or less

Oil E-500 or less

Oil G-50 or less

Oil I 50 or less

Compatibility test 1 2

The compounds obtained in each Example were tested for compatibility with HFC-134a / HFC-32. The compound (oil) obtained in each of the target examples was placed in a Pyrex test tube having an inner diameter of 8 mm and a length of 20 O mm, and the inside of the test tube was evacuated and cooled with liquid nitrogen. HFC-134a ZH FC-32 (70/30 wt%) (refrigerant) was filled in lg (the ratio of oil-Z refrigerant is 20/80 wt%). After charging the refrigerant, seal the test tube and set the temperature. After it was put into a regulated thermostat and the temperature reached equilibrium, the compatibility with the coolant was visually judged and the phase separation temperature at a low temperature was measured. Table 2 shows the phase separation temperatures at low temperatures.

Table 2

Compound Phase separation temperature (° C)

Oil A 50 or less

Oil B 150 or less

Oil C 150 or less

Oil D 50 or less

Oil E-500 or less

Oil G-500 or less

Oil I 50 or less

Compatibility test 1 3

The compatibility of the compounds obtained in each example with HFC-134a / HFC-32 no HFC-125 was tested. The compound (oil) obtained in each of the target examples was placed in a pyrex test tube having an inner diameter of 8 mm and a length of 20 O mm, and the test tube was evacuated and cooled with liquid nitrogen. HFC-134a / HFC-32 / HFC-125 (40/30/30 wt%) (refrigerant) filled with lg (oil Z refrigerant ratio is 20/80 wt% ). After charging the refrigerant, seal the test tube, put it in a temperature-controlled thermostat, and visually check the compatibility with the refrigerant after the temperature reaches equilibrium. Judgment was made and the phase separation temperature at a low temperature was measured. Table 3 shows the phase separation temperature at low temperatures.

Table 3

Compound Phase separation temperature (° c)

Oil A 50 or less

Oil B 150 or less

Oil C 150 or less

Oil D 50 or less

Oil E-500 or less

Oil G-500 or less

Oil I 50 or less

Compatibility test-4

The compounds obtained in each Example were tested for compatibility with HFC-134a / HFC-32HFC-23. The compound (oil) obtained in each of the target examples was placed in a Pyrex test tube with an inner diameter of 8 mm and a length of 200 mm, and the test tube was evacuated and cooled with liquid nitrogen. 1 g of HFC-13 4a ZHFC-32 / HFC-23 (70/25/5 wt%) (refrigerant) (The ratio of oil / refrigerant is 20/80 wt%) . After charging the refrigerant, the test tube was sealed, placed in a temperature-controlled thermostat, and after the temperature reached equilibrium, the compatibility with the refrigerant was judged visually and the phase separation temperature at low temperature was measured. Shows the phase separation temperature at low temperature Shown in 4

Table 4

Compound Phase separation temperature (° c) Oil A. 50 or less

Oil B 150 or less

Oil C 150 or less

Oil D 50 or less

Oil E-500 or less

Oil G-500 or less

Oil I 50 or less

Thermal stability test

Thermal stability tests were performed on the compounds obtained in each of the Examples and Comparative Examples. The compound (oil) obtained in each of the examples and comparative examples was placed in a Pyrex test tube with an inner diameter of 8 mm and a length of 200 mm, and copper and aluminum were further used as catalysts. One wire each (2 mm outside diameter, 50 mm length) (add water l OOO ppm to add water), vacuum the test tube, and use liquid nitrogen. Cooled and filled with HFC-134a (refrigerant) in lg (oil Z refrigerant ratio is 67 Z 33 wt%). After filling with the coolant, the test tube was sealed and placed in a temperature-controlled thermostat. After the temperature reached equilibrium, it was heated to that temperature, left for two weeks, and visually observed. Table 5 shows the results of the thermal stability test. 3

Table 5

Compound Without water With water

150 ° C 175 ° C 220 ° C 150 ° C 175 ° C 220 ° C Oil A 〇〇〇〇〇〇 Oil B 〇〇〇〇〇〇 Oil C 〇〇 One 〇〇〇 D Oil D 〇 E 〇〇〇〇 Oil E 〇〇〇〇〇〇 Oil G 〇〇〇〇〇 I Oil I 〇〇〇〇〇〇 Oil XXXXXXX Oil YXXXXXX

〇: No abnormality, X: Carbonized

Deoxidation test

Deoxidation tests were performed on the compounds obtained in each of the examples and comparative examples.

Deoxidation test 1

A solution (20 g) prepared by adding cone. HC1 to diglyme was placed in a 100 cc flask, and the compound (1 g) obtained in each Example and Comparative Example was further added. In addition, the mixture was stirred at room temperature for 10 hours. The total acid value at the start of the reaction and after the It was measured by the measurement method of S-K0700. Table 6 shows the measurement results.

Table 6

Total acid value (mg Κ Ο Η / g)

Compound At reaction start After reaction Oil A 4.26 1.08 Oil B 4.25 0.43 Oil C 4.2.4.01 Oil D 4.3.01 Oil E 4. 2 8 0.56 Oil G 4.2 5 2.48 Oil I 4.2 3 0.32 Oil X 4.3 5 4.3.5 Deoxidation test 1 2

The compounds (5 g) obtained in the respective Examples and Comparative Examples were placed in a 50 cc flask, and one drop of glacial acetic acid was further added, followed by stirring at 90 ° C. for 10 hours. The total acid value at the start of the reaction and after the end of the reaction were measured by the measuring method of JIS-K-070. Table 7 shows the measurement results. Table 7

Total acid value (mg g KOH / g)

At the beginning of the reaction After the reaction Oil A. 4.0.4.88 Oil B 4.39.0.5 1 Oil C 4.3.3.9 9 years old D 4. —3 3 3 0 2 oil E 4.3 9 0.72 oil G 4.35 5 3.28 oil I 4.33 0.43 oil X 4.3 1 4.3 1

Three

c autoclave ί:

The solution (20 g) prepared by adding HC 1 and the compound (1 g) obtained in each Example and Comparative Example were added, and the mixture was stirred at room temperature for 5 hours. The total acid value at the start of the reaction and after the end of the reaction were measured by the measuring method of JIS-K-070. Table 8 shows the measurement results. Table 8

Total acid value (mg g KOH / g)

At the start of compound reaction After reaction Oil A 4.2.0.82 Oil B 4.2.0.21 Oil C4.2.3.85 Oil D4.2.31.1 Oil E4 2 7 0 .6 3 Oil G 4.2 3 1 .28 Oil I 4 .28 0 .15 Oil X 4 .2 2 .4 2 2 Deoxidation test 1 4

To a 200 cc autoclave, add a solution (20 g) prepared by adding glacial acetic acid to dichloromethane and add the compound (1 g) obtained in each Example to 90 ° C. The mixture was stirred at C for 10 hours. The total acid value at the start of the reaction and after the end of the reaction was measured by the measuring method of JIS-K-070. Table 9 shows the measurement results. Table 9

Total acid (mg K 0 H / g)

Compound Start of reaction After reaction Oil A1.65 0.12 Oil B1.65 0.08 Oil C1.66 1.61 Oil D1.68 0.55 Oil E1.660.10 Oil G1.670.63 Oil I1-6.80.08 Oil X1

Each of the compounds obtained in Examples and Comparative Examples was subjected to an actual test using a refrigerant mixture of HFC-134a / HFC-32 / HFC-125.

The cleaning level (contamination level) in the system piping is set to two types, i.e., unwashed and twice-washed before operation, and the HFC- 1 3 4 a No.HFC-32 / HFC-125 (52/23/25 wt%) mixed refrigerant Te = 5 ° C, Tc = 55 ° C, S.H = After continuous operation for 2000 hours at an operating condition of 8 ° C and S.C = 5 ° C, the total acid value of each compound was measured. Measurement of total acid value The results are shown in Table 10.

Table 10

Total acid value after 2000 hours of operation— (mg KOH / g) Compound Cleaning level (contamination level)

'Wash twice =. ¾

N OT

Oil A 0.10 or less 0.10 or less Oil B 0.10 or less 0.10 or less Oil C 0.10 or less 0.10 or less Oil D 0.1.0 or less 0.10 or less Oil F 0.10 or less 0.10 or less Oil H 0.10 or less 0.10 or less Oil I 0.10 or less 0.10 or less Oil X 0.13.0.15

增 Viscosity test

The thickener and the oil E obtained in Example 5 were added to the oil D obtained in Example 4 and the viscosity (temperature: 40 ° C.) was measured using an E-type viscometer. The respective viscosities are shown in Table 11. 增 Viscosity additive viscosity

(t%) (c ρ) Poly (oxyethylene, oxypropylene)

(Average molecular weight: 250.50) 450.1 Poly (oxyethylene, oxypropylene) glycol

(Average molecular weight 400 000) 490.2 Polyoxyethylene glycol 4 14 1.6

(Average molecular weight 2 0 0 0)

Oil E 4 0 98.6 Oil G 8 0 6 0 0 Additive free (Oil D only) 2 5.5 Refining test

The treatment for lowering the total acid value of the oil D obtained in Example 4 was performed using various treating agents. Specifically, various treating agents were added to oil D (10 g), the mixture was stirred at room temperature for 2 hours, and after treating agents were filtered, the total acid value was measured by the measuring method of JISK-0,700. . The measurement results are shown in Table 12. Table 1 2

Treatment agent Treatment amount (wt%) Total acid value (mg KOHg)

Magnesia 3 0.0 0 0 2

No processing 0.0 6

Claims

General formula (1)

la

(Where n is an integer of 0 to 5; R ¹ is CF ₂ CF ₂ H or

H; R ² to R ^{7 each} represent an aliphatic group having 1 to 100 carbon atoms or a part of

An aliphatic group having 1 to 100 carbon atoms substituted by a fluorine atom (when R ^la is H, a fluorine atom is added to any of the groups R ² , R ^{5 and} R ⁶ ) A lubricating oil composition having excellent stability, comprising the compound [1] represented by:

2. A refrigerator oil composition having excellent stability, comprising the compound [1] according to claim 1.

3. A fluorine-based lubricating oil composition having excellent stability, comprising the compound [1] according to claim 1.

4. The compound [1] according to claim 1 and a general formula [2]

(Where m is an integer from 1 to 6; R ^lb and R ^le are

CF _n CF. H or H and R ^lb and R ^le are different

Two

11

R ⁸ to ^ are an aliphatic group having 1 to 100 carbon atoms or An aliphatic group having 1 to 100 carbon atoms, in which a moiety is substituted by a fluorine atom (when R ^lb and R ^le simultaneously represent H, the group may be either R ⁹ or R ^1Q ) 5) A lubricating oil composition having excellent stability, comprising a mixture of the compound [2] represented by)).

5. A refrigerator oil composition comprising the mixture according to claim 4 and having excellent stability.

6. A highly stable lubricating oil composition comprising the mixture according to claim 4 and an additive.

0 7. An excellently stable refrigerator oil composition comprising the mixture according to claim 4 and an additive.

8. A highly stable lubricating oil composition comprising the mixture according to claim 4 and a fluorine-containing additive.

9. A refrigerator oil composition having excellent stability, comprising the mixture according to claim 4 and a fluorine-containing additive.

10. A highly stable lubricating oil composition comprising the mixture described in claim 4 and a thickener.

1 1. A refrigerating machine oil composition comprising the mixture according to claim 4 and a thickener, and having excellent stability.

1 2. A highly stable lubricating oil composition comprising the mixture according to claim 4 and a fluorine-containing thickener.

1 3. Contains the mixture of claim 4 and a fluorine-containing viscosity agent Refrigerator oil composition with excellent stability.

1 4. (a) having from 1 to 5 carbon atoms, partially or completely, substituted by at least one atom of chlorine or fluorine; A composition comprising a saturated hydrocarbon having a standard boiling point in the range of 50 ° C and (b) the compound [1] according to claim 1.

15. (a) having from 1 to 5 carbon atoms, partially or completely, having from 1 to 5 carbon atoms substituted with at least one atom of chlorine or fluorine; A composition comprising a saturated hydrocarbon having a standard boiling point in the range of 50 ° C and (c) the mixture according to claim 4.

1 6. The component (a) is composed of 1,1,1,2—Tetrafluoroethane, 1,1,2,2—Tetrafluoroethane, Difluoromethane, 1,1,1,1, 15. The composition according to claim 14, wherein the composition is at least one compound selected from the group consisting of 2,2-pentafluorene.

1 7. The component (a) is composed of 1, 1, 1, 2—tetrafluroethane, 1, 1, 2, 2—tetrafluroethane, difluoromethane, 1, 1, 1, 1, 16. The composition according to claim 15, wherein the composition is at least one compound selected from the group consisting of 2,2-pentanofluorene.

1 8. Equation [3]: 0 CH ₂ 〇CF ₂ CF ₂ H

■ CH OCH ₀ —— C— CH ₀ OCF ₀ CF _n H

Δ Δ J L L L

CH ₂ OCF ₂ CF ₂ H

Compound represented by CH ₂ OCF ₂ CF ₂ H [3]

1 9. Equation [4]:

[4].

20. Equation [5]:

ΓΪ ₀し H

HCF ₂ CF ₂ — (0CH _o -C-CH ₂ --^ OCF ₂ CF H

CH ₂ OC F ₂ CF ₂ H

A compound [5] represented by the formula:

2 1. A lubricating oil composition having excellent stability, comprising the compound [1] according to claim 1, wherein n in the general formula [1] is an integer of 1 to 5.

2 2. The compound [1] according to claim 1 (where n in the general formula [1] is an integer of 1 to 5) or the compound [2] according to the claim 4 (where the general formula [2] m in 2 to 6 (Integer) as a thickener with excellent stability.

2 3. A refrigerating machine oil composition having excellent stability, comprising the compound [1] according to claim 1, wherein n in the general formula [1] is an integer of 1 to 5.

2 4. The compound [1] according to claim 1 (where n in the general formula [1] is an integer of 1 to 5) or the compound [2] according to the claim 4 (provided that the general formula [2] wherein m is an integer of 2 to 6) as a thickener.

25 General formula (6) in non-protonic polar solvent

13

( ^Where m is an integer of 1 to 6; R ^ltJ to R ¹⁵ are an aliphatic group having 1 to 100 carbon atoms) and tetrafluoroethylene. A method for producing a compound [1] according to claim 1 or a mixture of the compound [1] and the compound [2] according to claim 2, wherein the reaction is carried out using a base. .

2 6. Formula [7] in a non-protonic polar solvent:

19. The process for producing the compound [3] according to claim 18, comprising reacting the compound [7] represented by the formula with tetrafluoroethylene using a base.

2 7. Formula [8] in a non-protonic polar solvent:

10. The process for producing a compound [4] according to claim 19, comprising reacting the compound [8] represented by the formula with tetrafluoroethylene using a base.

2 8. Formula [8] in a non-protonic polar solvent:

CH ₂ CH ^

tHO CH ₂ ― C-CH H

CH ₂ OH

20. The method for producing a compound [5] according to claim 20, comprising reacting the compound [8] represented by the formula with tetrafluoroethylene using a base.

2 9. A mixture of the compound [1] and the compound [2] obtained by the production method according to claim 25 is an inorganic or organic compound. A method for purifying a mixture of a compound [1] and a compound [2], which comprises contacting with at least one kind of adsorbent.